CN110541302B - Method for modifying surface of paper-based material - Google Patents

Method for modifying surface of paper-based material Download PDF

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Publication number
CN110541302B
CN110541302B CN201910840504.7A CN201910840504A CN110541302B CN 110541302 B CN110541302 B CN 110541302B CN 201910840504 A CN201910840504 A CN 201910840504A CN 110541302 B CN110541302 B CN 110541302B
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base material
paper
paper base
fiber
initiator
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CN201910840504.7A
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CN110541302A (en
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李群
刘蓉蓉
游紫
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Tianjin University of Science and Technology
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Tianjin University of Science and Technology
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
    • D06M14/04—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Graft Or Block Polymers (AREA)
  • Paper (AREA)

Abstract

The invention discloses a method for modifying the surface of a paper-based material. The method is basically characterized in that fiber materials with high specific surface area and catalyst adsorption capacity, such as nano-cellulose, high-beating-degree fibers, synthetic fibers and the like, are used as initiator carriers and are adsorbed on the surface of the paper-based material fibers to form initiation sites, and grafting hydrophobic modification is completed on the surface of the paper-based material. The carrier fiber loaded with the initiator is added into the paper base material, is tightly combined with the paper base material, covers the surface of the paper base material, has a great specific surface area and abundant surface hydroxyl (-OH), and has more initiation sites in the free radical polymerization reaction, so that the grafting rate of the functional monomer is improved in the grafting process. The modification reaction mainly occurs on the surfaces of the nanofiber containing the initiator and the paper base material, and the damage and negative influence on the structure of the paper base material can be reduced while the surface modification of the paper base material is realized.

Description

Method for modifying surface of paper-based material
Technical Field
The invention belongs to cellulose fiber free radical polymerization grafting modification by taking a Fenton reagent as an initiator. In particular to a method for completing grafting functional modification by using fiber materials with high specific surface area and catalyst adsorption capacity, such as nano-cellulose, high-beating-degree fibers, synthetic fibers and the like as initiator carriers to adsorb on the surface of a paper-based material to form initiation sites.
Background
The paper-based functional material takes natural plant fibers as main raw materials, is an important direction for transformation of the traditional paper making industry, and one of the main modification means is to introduce various functional groups to adapt to different requirements through graft modification treatment on cellulose-based materials.
In the chain polymerization reaction of the monomers, the cellulose fiber is easy to cause fiber swelling caused by the fact that the grafting monomers enter the fiber, the fiber structure is damaged, and the fiber strength is damaged. In order to ensure the characteristics and strength of the paper base material and reduce ineffective grafting and waste of the initiator and the monomers in a reaction system, a fiber material (such as nano-fibrils, microfibrillated cellulose, inorganic fibers or aramid fibers and the like) capable of loading the initiator is added into the cellulose-based material and is adsorbed and covered on the fiber material, so that the free radical polymerization reaction is mainly limited on a carrier containing the initiator and the surface of the paper base material.
Fenton reagent (Fe) is selected 2+ +H 2 O 2 ) As an initiator, the initiator is cheap and easy to obtain, takes water as a medium in the reaction, has mild conditions, is clean and environment-friendly, and can be suitable for industrial large-scale use and production. The carrier of iron ions is made of fiber with large specific surface area and abundant surface hydroxyl (-OH), and the number of exposed hydroxyl on the surface of the carrier or the reaction capacity (such as beating degree and fibrosis degree of the carrier fiber) can be adjusted to control the freedomThe number of initiation sites in the base polymerization reaction and the grafting rate of the functional monomer, and the effect of blending the paper-based functional material.
The method is suitable for various cellulose-based materials such as various filter papers (selective filter paper), packaging paper, flame retardant paper and various papers and products thereof with surface modification requirements.
Disclosure of Invention
The invention aims to provide a free radical polymerization grafting modification method for realizing the surface of paper pulp fibers by taking fiber materials with high specific surface area and adsorption capacity, such as nano-cellulose, high-beating-degree fibers, synthetic fibers and the like as carriers and loading a free radical polymerization initiator to fix the initiator on the surface of the paper base material, and introducing functional groups on the fibers to manufacture a composite paper base functional material.
The invention is implemented by the following technical scheme:
the carrier takes the nano-fibrils as an example, the nano-fibrils are soaked in ferrous sulfate solution and are fully washed by a centrifugal method to remove free iron ions. Taking sulfate bleached softwood pulp as an example of a paper-based material raw material, adding nanofibrils accounting for 5-10% of the mass of primary pulp, and fully mixing and stirring to enable the nanofibrils loaded with iron ions to be uniformly adsorbed on the surface of fibers. Using water as reaction medium, adding paper pulp fiber treated by 0.5-5% of total mass of solvent, 2-10% of monomer (vinyl monomer such as methyl acrylate, ethyl methacrylate, etc.), 0.1-2% of emulsifier, introducing nitrogen to remove oxygen, heating to 60-80 deg.C, and stirring for 15min. Adding 0.01-0.1% of hydrogen peroxide for reaction for 0.5-1.5 h, forming a Fenton redox system with ferrous ions loaded in the nano-fibrils to generate free radicals, and performing free radical grafting reaction on the fiber surface to obtain the hydrophobic modified paper-based material.
Compared with the prior art, the invention has the following advantages:
compared with hydrophobic modified fibers such as an impregnation method and a vapor deposition method, the nanofibrils loaded on the surface of the cellulose fiber have richer surface hydroxyl (-OH) groups and have more initiation sites in a free radical polymerization reaction, so that the grafting rate of a hydrophobic monomer can be greatly improved, and the hydrophobic effect is enhanced. Meanwhile, the grafting reaction mainly occurs on the nanofibrils containing the initiator and on the surface of the fiber, so that the damage to the fiber structure can be reduced.
Detailed Description
The best mode for carrying out the invention is described in further detail below by way of specific examples.
Taking 100 tons/day of sulfate bleached softwood pulp as an example of a production process of a surface modified paper-based functional material, the specific implementation mode is as follows:
the carrier takes the nano-fibrils as an example, the nano-fibrils are soaked in ferrous sulfate solution and are fully washed by a centrifugal method to remove free iron ions. The paper base material takes 100 tons of sulfate bleached softwood pulp as a raw material, 6 tons of iron ion loaded nano fibrils (absolutely dry) are added, and the mixture is fully mixed and stirred, so that the iron ion loaded nano fibrils are uniformly adsorbed on the surfaces of fibers. Adding 200 tons of monomers (methyl acrylate and ethyl methacrylate) and 8 tons of emulsifier, adding a proper amount of clear water to adjust the concentration of the slurry to be 2 percent, introducing nitrogen to remove oxygen, heating to 60 ℃, and stirring for 15min. Adding 2.5 tons of hydrogen peroxide, fully stirring and reacting for 1 hour to obtain the surface hydrophobic modified paper base material.
Compared with the prior art, the invention has the following advantages:
(1) The addition of fiber materials (such as nano fibrils, microfibrillated cellulose, inorganic fibers or aramid fibers and the like) capable of loading an initiator to a cellulose-based material limits radical polymerization reactions mainly to carriers containing the initiator and the surface of the paper-based material. Damage and negative effects on the fiber structure can be reduced.
(2) controlling the number of initiation sites in the free radical polymerization reaction and the grafting rate of the functional monomer by adjusting the number of exposed hydroxyl groups on the surface of the carrier or the reaction capability (such as the beating degree of carrier fibers, the degree of fibrillation and the like), and blending the effect of the paper-based functional material.

Claims (1)

1. A method for modifying the surface of a paper-based material is characterized by comprising the following preparation steps:
(1) Soaking the nano-fibril, the high-beating-degree fiber, the inorganic fiber or the aramid fiber in a ferrous sulfate solution, fully washing by a centrifugal method, and removing free ferrous ions to prepare carrier fiber;
(2) Sulfate bleached softwood pulp is used as a paper base material, carrier fibers with 6% of the original mass of the paper base material are added, and the mixture is fully mixed and stirred, so that the carrier fibers loaded with ferrous ions are uniformly adsorbed on the surface of the paper base material; adding 2 mass percent of the treated paper substrate, 4 mass percent of methyl acrylate vinyl monomer or ethyl methacrylate vinyl monomer and 0.16 mass percent of emulsifier into a reactor by taking water as a reaction medium, introducing nitrogen to remove oxygen, heating to 60 ℃, and stirring for 15min;
(3) Adding 0.05% of hydrogen peroxide for decomposition to generate free radicals, performing free radical grafting reaction on the surface of the paper base material, and fully stirring for reaction for 1h to obtain the functionalized modified paper base material.
CN201910840504.7A 2019-09-06 2019-09-06 Method for modifying surface of paper-based material Active CN110541302B (en)

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Application Number Priority Date Filing Date Title
CN201910840504.7A CN110541302B (en) 2019-09-06 2019-09-06 Method for modifying surface of paper-based material

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CN110541302B true CN110541302B (en) 2022-12-13

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Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112342816B (en) * 2020-11-02 2022-08-09 天津科技大学 Protection technology for paper pulp in oxygen delignification

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014163002A (en) * 2013-02-22 2014-09-08 Arakawa Chem Ind Co Ltd Surface sizing agent for paper making and paper coated with the sizing agent
CN109898321A (en) * 2019-02-27 2019-06-18 天津科技大学 It is a kind of to load Fe using carboxymethyl cellulose2+To the method for pulp fiber surface oxidation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014163002A (en) * 2013-02-22 2014-09-08 Arakawa Chem Ind Co Ltd Surface sizing agent for paper making and paper coated with the sizing agent
CN109898321A (en) * 2019-02-27 2019-06-18 天津科技大学 It is a kind of to load Fe using carboxymethyl cellulose2+To the method for pulp fiber surface oxidation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Green and Efficient Synthesis of Dispersible Cellulose Nanocrystals in Biobased Polyesters for Engineering Applications;Stephen Spinella et.al.;《ACS Sustainable Chem. Eng.》;20160401(第4期);第2517-2527页 *

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